入门。简单液体和溶液的结构和性质综述

J. Rowlinson
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引用次数: 27

摘要

简单液体的结构主要是由分子间的排斥力决定的。引力的作用可以通过摄动处理来发现,范德华的摄动处理是其原型,巴克和亨德森的摄动处理是最近的。排斥力在决定不同大小的球形分子混合物的结构时同样重要,这种混合物的结构与未混合液体中的结构大不相同。辛格最近的蒙特卡罗计算可以作为判断混合理论的标准,并且表明,只有那些公正地对待这种结构差异的理论才是适当的。有人认为,在决定自由能时,分子的形状往往不如它们的大小重要,因此,正构烷烃或线性聚合物溶液的理论在其结果中与不同大小的球形分子混合物的理论没有很大的不同。
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Introductory. Structure and properties of simple liquids and solutions: a review
The structure of a simple liquid is determined primarily by the repulsive forces between the molecules. The effects of the attractive forces can be found by perturbation treatments, of which that of van der Waals is the prototype, and that of Barker and Henderson the most recent. The repulsive forces are equally important in determining the structures of mixtures of spherical molecules of different sizes—structures which are quite different from those found in the unmixed liquids. Recent Monte Carlo calculations by Singer can be used as a standard by which theories of mixtures can be judged, and it is shown that the only adequate theories are those which do justice to this difference in structures. It is suggested that the shape of molecules is often of less importance than their size in determining the free energy, and hence that theories of solutions of n-alkanes or of linear polymers do not, in their results, differ greatly from those of mixtures of spherical molecules of different sizes.
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